Sizing composition for glass strands, process using this composition and resulting products

ABSTRACT

The present invention relates to a sizing composition for glass strands composed of a solution with a viscosity of less than or equal to 400 cP comprising less than 5% by weight of solvent and comprising at least one thermally polymerizable base system, the said base system comprising at least 60% by weight of components with a molecular mass of less than 750 and comprising at least 60 % by weight of a mixture: 
     of component(s) exhibiting at least one epoxy reactive functional group, 
     and of component(s) exhibiting at least one anhydride reactive functional group. 
     The invention also relates to a process using this composition and to the strands obtained according to this process and coated with the said composition.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a sizing composition for glass strands,this composition reacting to heat. The present invention also relates toa process for the production of reinforcing glass strands using thiscomposition as well as to the glass strands obtained and to thecomposites produced from the strands.

In the continuation of the text, “polymerization”, “to polymerize”,“polymerizable” and the like are understood to mean “polymerizationand/or crosslinking”, “to polymerize and/or to crosslink”,“polymerizable and/or crosslinkable” and the like respectively.

2. Description of the Background

Reinforcing glass strands are manufactured in a known way from moltenglass streams flowing from die orifices. These streams are drawn in theform of continuous filaments and then these filaments are gathered intobase strands, which are then collected.

Before they are gathered together in the form of strands, the filamentsare coated with a size by passing over a sizer device. This depositionis necessary for the production of the strands and makes it possible tocombine them with other organic and/or inorganic materials to producecomposites.

The size serves, in the first place, as lubricant and protects thestrands from the abrasion resulting from the high-speed friction of thestrands over various devices during the abovementioned process.

The size can also ensure, in particular after polymerization, theintegrity of the abovementioned strands, that is to say the binding ofthe filaments to one another within the strands. This integrity is inparticular sought after in textile applications where the strands aresubjected to strong mechanical stresses. Indeed, if the filaments showlittle attachment to one another, they break more readily and disruptthe operation of the textile machinery. Strands that do not exhibitintegrity are moreover regarded as difficult to handle.

The size also facilitates the wetting and/or the impregnation of thestrands by materials to be reinforced and helps in the creation of bondsbetween the said strands and the said materials. The mechanicalproperties of the composites obtained from the material and the strandsdepend in particular on the quality of the adhesion of the said materialto the said strands and on the ability of the said strands to be wettedand/or to be impregnated by the said material.

The sizing compositions used must be sufficiently stable and compatiblewith the drawing rates of the filaments which have to pass through them(several tens of meters per second). They must in particular resist theshearing induced by the passage of the filaments and properly wet theirsurface at the said rates. In the case where they thermally polymerize,they must exhibit a reaction temperature which is sufficiently high toremain stable at the die. It is also desirable for these compositions toexhibit, after polymerization, a maximum degree of conversion (thisdegree corresponding to the ratio of the level of functional groupswhich have reacted in the size after heat treatment to the level, in thesize, before heat treatment of reactive functional groups capable ofreacting), in order to guarantee in particular that sized strands ofconstant quality are obtained (a size exhibiting a degree of conversionwhich is much below the theoretical degree expected being capable ofchanging overtime).

The majority of sizes currently used are aqueous sizes which are easy tohandle but which have to be deposited in large amounts on the filamentsin order to be effective. The water generally represents 90% by weightof these sizes (in particular for reasons of viscosity), whichnecessitates the drying of the strands before they are used asreinforcers, it being possible for the water to be harmful to the goodadhesion between the strands and the materials to be reinforced. Thesedrying operations are lengthy and expensive, must be adapted to themanufacturing conditions of the strands and their efficiency is notalways optimum. When they are carried out during the fibre-drawingoperation (that is to say before collecting the strands obtained bygathering together the filaments), on the filaments (WO 92/05122) or onthe strands (U.S. Pat. No. 3,853,605), they require the installation ofdrying devices at each die and when they are carried out on the strandwound packages, they bring about risks of uneven and/or selectivemigration of the components of the size within the wound packages(aqueous sizes already having a tendency to spread themselves unevenlyover the strands because of their nature) and optionally phenomena ofcolouring of the strands or of deformation of the wound packages. Thedeformation of the wound packages is also observed, in the absence ofdrying, on straight-edged wound packages (rovings) of fine strands (thatis to say exhibiting a “count” or “mass per unit length” of 300-600 tex(g/km) or less) coated with aqueous sizes.

A few exceptional patents describe non-aqueous sizes but these sizesgenerally involve organic solvents which are problematic to handle andwhich can, because of their toxicity, harm the health of people in thevicinity and/or pose problems of viscosity which it is appropriate tosolve by heating these sizes (U.S. Pat. No. 4,604,325) or by addingsuitable agents (U.S. Pat. No. 4,609,591). These sizes also oftenrequire the installation of specific devices below each die; it is inparticular necessary, when the strands are collected in the form ofwound packages, to treat the strands before obtaining the wound packagesin order to prevent the turns of each wound package from sticking to oneanother, this sticking phenomenon making it difficult to unwind thestrands. These treatments, the effectiveness of which depends on theoperating conditions, consist, for example, in polymerizing the size bysubjecting the sized strands to the effect of ultraviolet radiation inorder to confer on them a satisfactory integrity and to make it possibleto handle them (U.S. Pat. No. 5,049,407). The polymerized size, however,prevents the filaments from sliding with respect to one another, thisabsence of mobility resulting in the shattering, by mechanicaldegradation of the size, of the strands when they are cut and it beingpossible for this absence of mobility to cause problems in textileapplications where the strands used must both exhibiyt integrity and beflexible.

SUMMARY OF THE INVENTION

The subject of the present invention is an improved sizing compositionwhich does not exhibit the abovementioned disadvantages, thiscomposition being intended to coat glass strands and being capable ofpolymerizing under the effect of heat, this composition making it easyto handle the sized strands, even before polymerization, and conferringon them a flexibility compatible with their subsequent treatments, thiscomposition conferring good integrity on the strands afterpolymerization and exhibiting a high degree of conversion, thiscomposition in addition efficiently protecting the strands fromabrasion, conferring on them the possibility of being combined withvarious materials to be reinforced for the purpose of producingcomposite items exhibiting good mechanical properties, beingparticularly stable, in particular at the die, and being compatible withthe drawing rates of the filaments.

Another subject of the present invention is an improved process for themanufacture of sized glass strands as well as sized glass strands whichare easy to handle and which exhibit improved characteristics, the saidstrands being capable of efficiently reinforcing organic and/orinorganic materials for the preparation of composites.

The sizing composition according to the invention is composed of asolution with a viscosity of less than or equal to 400 cP comprisingless than 5% by weight of solvent and comprising a thermallypolymerizable base system, the said base system comprising at least 60%by weight of components with a molecular mass of less than 750 andcomprising at least 90% by weight of a mixture:

of component(s) exhibiting at least one epoxy reactive functional group,

and of component(s) exhibiting at least one anhydride reactivefunctional group.

The invention also relates to a process for the production of sizedglass strands according to which a multiplicity of molten glass streams,flowing from a multiplicity of orifices arranged at the base of one or anumber of dies, is drawn in the form of one or a number of sheets ofcontinuous filaments and then the filaments are gathered together in oneor a number of strands which are collected on a moving support, the saidprocess comprising the deposition at the surface of the filaments,during drawing and before gathering together the filaments into strands,of the sizing composition defined above.

The invention further relates to strands coated with a size exhibitingthe composition defined above and/or obtained according to the processmentioned above.

DETAILED DESCRIPTION OF THE INVENTION

Subsequently, “epoxy component(s)” and “anhydride component(s)” isunderstood to mean “component(s) exhibiting at least one epoxy reactivefunctional group” and “component(s) exhibiting at least one anhydridereactive functional group” respectively.

In the composition according to the invention, the possible solvents areessentially organic solvents necessary for dissolving certainpolymerizable compounds. The presence of these solvents in a limitedamount does not require specific treatments to remove them; in themajority of cases, the sizes according to the invention are, moreover,entirely free of solvent, that is to say of compounds which act solelyas solvent in the solution.

Due to its low viscosity (less than or equal to 400 cP and preferablyless than or equal to 200 cP), the sizing composition according to theinvention is compatible with the conditions for producing glass strandsimposed by the direct process, the viscosity of the composition beingchosen as a function of the drawing rate and of the diameter of thefilaments caused to pass through it. The composition according to theinvention also exhibits a wetting rate on the strand Compatible with thedrawing rate of the strands.

“Thermally polymerizable base system” according to the invention shouldBe understood as meaning the compound or compounds essential to thesizing And having the essential function of participating in thestructure of the polymerized size, these compounds being capable ofthermally polymerizing. As a general rule, the base system representsbetween 60 and 100% by weight of the sizing composition according to theinvention, mainly between 70 and 99.5% by weight of the composition and,in the majority of cases, between 75 and 90% by weight of thecomposition.

The base system is mostly composed (preferably from 80% by weight and upto 100% by weight in the majority of cases) of epoxy component(s) and ofanhydride component(s), the use of this mixture of components making itpossible to obtain, after polymerization, epoxy-anhydride (polyester)copolymers as the major participants in the structure of the polymerizedsize, the properties of the sized strands depending directly on thisstructure.

In addition, the base system comprises a majority (preferably at least70-75% by weight and up to 100% by weight) of component(s) with amolecular mass of less than 750, this/these component(s) normally mostly(and in the majority of cases, entirely) forming part of theabovementioned epoxy and anhydride components.

Preferably and in general according to the invention, the componentswith a molecular mass of less than 750 mentioned above have molecularmasses of less than 500. Likewise, in the majority of cases according tothe invention and preferably, these components are monomers (mono- orpolyfunctional, as explained subsequently) but the base system can alsocomprise components with a molecular mass of less than 750 in the formof oligomers or of polymers containing partially polymerized functionalgroups.

According to certain embodiments, the base system according to theinvention can optionally comprise a small proportion of component(s)participating in the structure of the polymerized size but notexhibiting epoxy or anhydride functional groups and/or exhibiting ahigher molecular mass.

According to the preferred embodiment of the invention which makes itpossible to obtain particularly satisfactory results, the base system iscomposed solely of components exhibiting at least one epoxy or anhydridereactive functional group and/or, optionally, is composed solely ofcomponents with a molecular mass of less than 750.

The epoxy or anhydride components which can be used in the base systemcan exhibit one (monofunctional components) or a number of identicalreactive functional groups (polyfunctional components) among epoxy andanhydride functional groups.

The epoxy component or components of the base system can be inparticular one or a number of the following components: alkyl glycidylether with a C₄-C₁₆ aliphatic chain or the like; cresyl- or phenyl- ornonylphenyl- or p-tert-butylphenyl- or 2-ethylhexyl-glycidyl ether andthe like; limonene epoxide; cyclohexene monoxide; glycidyl ester ofversatic acid or of neodecanoic acid; and the like (the above componentsbeing monofunctional components); 1,4-butanediol or neopentyl glycol orresorcinol or cyclohexanedimethanol or 1,6-hexanediol ordibromoneopentyl glycol diglycidyl ether and the like; diepoxidizedderivative of bisphenols A or F; 3,4-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate; bis(3,4-epoxycyclohexyl) adipate,polyglycol diepoxide; diglycidyl ester of hexahydrophthalic anhydride;diglycidylhydantoin;2-(3,4-epoxycyclohexyl)-5,5-spiro-(3,4-epoxycyclohexyl)-m-dioxane,vinylcyclohexene dioxide; trimethylolethane or trimethylolpropane ortrisphenylolmethane triglycidyl ether and the like; triglycidyl ether ofpalm oil; triglycidyl ether of para-aminophenol;tetra(para-glycidoxyphenyl)ethane;4,4′-(diglycidylamino)diphenylmethane; polyglycidyl ether of analiphatic polyol, epoxidized polybutadiene; epoxycresol novolak orepoxyphenol novolak resin; triglycidyl isocyanurate;N,N,N′,N′-tetraglycidyl-α,α′-bis(4-aminophenyl)- orN,N,N′,N′-tetraglycidyl-α,α′-bis(4-amino-3,5-dimethylphenyl)-p-diisopropylbenzeneand the like; and the like (these components being polyfunctionalcomponents).

As a general rule according to the invention, the proportion of epoxycomponent(s) of the base system is between 15 and 85% by weight of thesizing composition, mainly between 25 and 70% by weight approximately ofthe sizing composition. In the majority of cases, it is between 35 and60% by weight of the sizing composition.

The anhydride component or components of the base system can be inparticular one or a number of the following components:methylbicyclo[2.2.1 ]heptene-2,3-dicarboxylic anhydride;hexahydrophthalic anhydride; dodecylsuccinic anhydride; phthalicanhydride; 1,4,5,6,7,7-hexa-chlorobicyclo[2.2. 1]hept-5-ene-2,3-dicarboxylic anhydride;endo-cis-bicyclo[2.2.1]heptene-2,3-dicarboxylic anhydride;tetrachlorophthalic anhydride; pyromellitic dianhydride;1,2,3,4-cyclopentanetetracarboxylic dianhydride; polyazelaicpolyanhydride; polysebacic anhydride; glutaric anhydride; oralternatively other polyester anhydride; bromo- or dibromophthalicanhydride; cyclic sulphopivalic anhydride; bicyclodicarboxylicanhydride; diphenoxyphosphinylsuccinic anhydride; anhydride of2-alkyleneglutaric acid; poly(cycloaliphatic anhydride); styrene-maleicanhydride; cyclooctadiene-maleic anhydride; perchlorocoumalin-maleicanhydride; myrcene monoepoxide-maleic anhydride;cyclohexadiene-dicarboxylic-maleic anhydride;poly(cyclopentadienyl)-maleic anhydride; trimellitic anhydridederivative (bistrimellitic anhydride of neopentyl glycol, product of theacidolysis of a tricarboxylic anhydride and of an ester or of an amine,oxyalkylated derivative of trimellitic anhydride); anhydride ofphenylenebis(3-butanedicarboxylic acid); dianhydride ofbenzophenone-tetracarboxylic acid; dianhydride ofphenylalkyl-pentanetetracarboxylic acid; dianhydride ofalkyl-substituted tricyclodecanecarboxylic acid; dianhydride ofdicarboxytetrahydronaphthalenesuccinic acid; and the like.

As a general rule according to the invention, the proportion ofanhydride component(s) of the base system is between 5 and 65% by weightof the sizing composition, mainly between 10 and 55% by weightapproximately of the composition. In the majority of cases, it isbetween 15 and 45% by weight of the sizing composition.

Preferably, according to the invention, the components of the basesystem and their levels (or rates or amounts) within the base system arechosen so that the ratio r of the number of anhydride reactive sites tothe number of contrasting epoxy reactive sites is between 0.2 and 6 (anepoxy functional group counting as one epoxy reactive site and ananhydride functional group counting as two anhydride reactive sites), soas to make possible satisfactory polymerization of the sizingcomposition, in particular by formation of epoxy-anhydride (polyester)copolymers, during the polymerization heat treatment. In the majority ofcases according to the invention, this ratio r is between 0.3 and 4 and,preferably, it is greater than 0.4 and less than or equal to 2.0approximately, so as to promote the formation of more stableepoxy-anhydride copolymers of diester type (the formation of copolymersof monoester type not, however, being excluded when the ratio r isgreater than 1 and it being possible for the formation of copolymers ofmonoester type to exhibit advantages in the reinforcement of certainmatrices).

In one embodiment of the invention, the sizing composition comprises, inaddition to the base system, at least one specific catalyst whichpromotes the polymerization of the size under the effect of heat byfacilitating the opening of the anhydride and/or epoxy functionalgroups, mainly in the case where the anhydride component or componentsof the base system have little reactivity and/or optionally in the casewhere the base system is devoid of cycloaliphatic epoxy components. Thiscatalyst is preferentially chosen from amino derivatives, such astrialkylamines, hexamethylenetetramine, aniline/formaldehydecondensation products, substituted aniline/aliphatic aldehyde(anhydrobutyraldehyde/toluidine) condensates, epoxy-amines(N-(2,3-diepoxypropyl)aniline), basic tertiary amines,N,N-dialkylalkanolamines, amino salts of polyacids, quaternary ammoniumsalts, quaternary imidazoline salts, dicyanodiamide, and the like, orfrom derivatives of boron and of phosphorus, such as ammoniumorganoboron salts, trialkanolamine borates, fluoroborates,organosubstituted phosphines, and the like, or from metal derivatives,such as tin tetrachloride (SnCl₄), divalent tin salts, metal chelatescontaining epoxide groups, magnesium, barium, zinc or cadmium oxides,and the like, or alternatively from alcohols.

The polymerization of the epoxy and anhydride components can also beinitiated by the presence of water (even in the form of traces), by thehydroxyl or carboxyl groups of components of the size (presence, forexample, of hydrolysed silanes), by the moisture in the surrounding air,and the like. In the absence of catalyst(s) as defined above, the ratior is in addition generally less than 3 and preferably less than 2.

The level of specific components defined above which act solely ascatalysts in the sizing composition is less than 3% by weight of thesizing composition, in the majority of cases less than 1% by weight and,preferably, is less than or equal to 0.5% by weight of the sizingcomposition. The presence of a catalyst which promotes the opening ofthe anhydride components makes it possible to use less reactiveanhydrides and to lower the polymerization temperature of the size, asexplained subsequently. In the case of highly reactive anhydridecomponents, such as phthalic anhydride, maleic anhydride or succinicanhydride, the presence of a catalyst is, in contrast, generallyavoided.

In addition to the base structure and the specific catalyst(s), thecomposition according to the invention can comprise additives in smallamounts, these additives giving specific properties to the sizingcomposition but not being essential participants in the structure of thesize, in contrast to the base system. Even if these additives are to bedistinguished from the base system, they may nevertheless be thermallypolymerizable, like the compounds of the base system.

The composition according to the invention can thus comprise, asadditive, at least one coupling agent which makes it possible to attachthe size to the glass, the proportion of the coupling agent or agentsbeing between 0 and 25% by weight of the size and preferably being lessthan or equal to 20% by weight of the size. These agents can be one or anumber of the following components: silanes, such asγ-glycidoxypropyltrimethoxysilane,γ-methacryloyloxy-propyltrimethoxysilane, polyethoxylated-propoxylatedtrimethoxysilane, γ-acryloyloxypropyltrimethoxyilane,vinyltrimethoxysilane, phenylaminopropyltrimethoxy-silane, and the like;or titanates, zirconates, siloxanes, and the like.

The composition according to the invention can also comprise, asadditive, at least one film-forming agent which acts solely as slipagent and which facilitates fibre-drawing, in proportions of between 0and 10% by weight and preferably less than or equal to 5% by weight. Thepresence of this agent or agents prevents significant friction of thefilaments on the sizing device when the filaments are drawn at a highrate (more than 40 m/s) and/or when they are very fine, these agentsbeing, however, expensive and it being possible for these agents toresult in a diminuation in the mechanical characteristics of thecomposites. These fibre-drawing agents can be one or a number of thefollowing components: silicones, siloxanes or polysiloxanes, such asglycidyl(n)polydimethylsiloxane, α,ω-acryloyloxypolydimethylsiloxane,and the like, silicone derivatives, such as silicone oils, and the like.

The composition according to the invention can also comprise, asadditive, at least one textile processing agent acting essentially aslubricant, in proportions of between 0 and 15% by weight and preferablyof between 0 and 8% by weight. These textile agents can be one or anumber of the following components: fatty esters (optionally ethoxylatedor propoxylated), glycol derivatives (in particular of ethylene or ofpropylene glycol), such as isopropyl or cetyl palmitates, isobutylstearates, decyl laurates, ethylene glycol adipates, polyethyleneglycols or polypropylene glycols with a molecular weight of less than2000, isopropyl stearates, and the like.

The size can also comprise, as additive, at least one agent for adaptingto the materials to be reinforced, in the case of cement materials inparticular.

The sizing composition according to the invention efficiently protectsthe strands from abrasion, is stable, in particular at the die (thecomposition according to the invention not truly polymerizing before100° C. and being subjected at the die to temperatures not exceeding 70°C.), is compatible with the drawing rates of the filaments and does notrequire recourse to a drying operation before polymerization or recourseto a specific treatment between the deposition on the strand and theoperation of collecting the sized strands.

Moreover, when the composition according to the invention is depositedon the filaments during drawing, it spreads out very quickly over thewhole of their surface and forms a true protective film for each ofthem. The strand obtained by gathering together the filaments and whichis coated with the thermally untreated composition (that is to say notyet polymerized) is thus composed of a bundle of sheathed filamentswhich can slide over one another, this strand then exhibiting highflexibility, which is particularly advantageous in the case where thisstrand is intended to be cut, the sheathing of the filaments in additionoffering additional protection against abrasion. Such a strand does notexhibit integrity in the ordinary meaning of the term, that is to saythat it is not composed of filaments attached to one another by virtuein particular of an adhesive binding caused by one or a number ofconstituents of the size, such as can be caused by sticking film-formingagents present in significant amounts in a size. Despite this, thisstrand coated with the not yet polymerized composition is easy to handleand, when it is wound in the form of wound packages, can easily beextracted from the wound packages without having subjected the sizebeforehand to a polymerization treatment. The strands coated with thenot yet polymerized sizing composition have, moreover, a very goodaptitude towards wetting and towards impregnation by materials to bereinforced, it thus being possible for the impregnation to take placemore rapidly (gain in productivity) and the composites obtained thusexhibiting a more homogeneous appearance and some improved mechanicalproperties.

The integrity proper of the strands by adhesive binding of the filamentsconstituting them is obtained after polymerization of the sizingcomposition by the effect of heat. This integrity is sought for withrespect to the strands which have to be subjected to strong mechanicalstresses, for example in textile applications (the ratio r of thecomposition is preferentially between 0.5 and 2 approximately when thestrands are intended to be woven), or, if appropriate, after cutting,with respect to the cut strands intended to reinforce organic and/orinorganic materials. It is preferable, in such cases, to carry out thepolymerization of the size before, respectively, using the strands intextile applications or combining the cut strands with a material to bereinforced.

The integrity obtained after polymerization of the size is particularlyimportant whereas the level of size on the strands is relatively low(the loss on ignition of the strands coated with the sizing compositionand/or obtained according to the process of the invention not exceeding3% by weight). The amount of sizing composition which has to bedeposited on the strands in order to be effective is advantageously notimportant and makes it possible, however, to obtain strands exhibitingvery good characteristics, including integrity (the integrity obtainedbeing high even for levels of size on the filaments of the order of 0.6%by weight).

The sizing composition according to the invention also exhibits, afterpolymerization, a maximum degree of conversion, the degree of conversionof the anhydride components being, for example, close to 100% when theratio r is less than approximately 1.

Moreover, it is observed, surprisingly, that properties such as thetensile strength of the strands according to the invention are better,after the beginning of ageing in a humid environment, than thoseobtained before ageing of the strands.

The strands according to the invention can advantageously be combinedwith various materials to be reinforced for the purpose of producingcomposite items exhibiting good mechanical properties. The compositionaccording to the invention makes the strands particularly compatiblewith the materials to be reinforced, in particular with organicmaterials and in particular epoxy materials but also with inorganicmaterials such as cement materials. It also makes possible theimpregnation of the sized strands by the material to be reinforced. Thiscomposition is particularly suitable for the production of continuousstrands collected in the form of rovings, cakes, cops, mats, and thelike or for the production of cut strands, these different strands beingcomposed of filaments with a diameter which can range from 5 toapproximately 24 microns. The sizing composition according to theinvention is in particular suited to the production of fine strands(with a count of less than 600 tex) collected in the form of rovings, incontrast to conventional aqueous sizes.

The sizing composition according to the invention is advantageouslydeposited during the process according to the invention on filamentsintended to be collected into strands and is then polymerized under theeffect of a heat treatment, the said treatment taking placeindependently of the fibre-drawing operation (devices thus not beingnecessary below each die) and it being possible for the said treatmentto be carried out at different stages of the process afterfibre-drawing.

The heat treatment can in particular be carried out on the collectedstrands or during the preparation of a composite by combining the sizedstrands with an organic material. In the case where the strands obtainedare collected in the form of wound packages, the heat treatment can becarried out on the strand wound packages prior to the use of thestrands, in particular in textile applications. If the heat treatment iscarried out with respect to the strand wound packages before unwindingthe strands, it is desirable for the strand turns constituting the saidwound packages to exhibit a crossing angle at least equal to 1.50 inorder to prevent adhesive bonding between turns via the polymerizedsize, these adhesive bondings making it difficult to unwind the strands.

The strands obtained after gathering together the filaments can also becollected on receiving supports in translational motion. They can indeedbe projected, by a device which is also used to draw them, towards thecollecting surface moving transversely to the direction of the projectedstrands, for the purpose of obtaining a sheet of intermixed continuousstrands, known as a “mat”, in which case the heat treatment can becarried out on the strands spread out over the collecting surface. Ifappropriate, a binder (it being possible for this binder optionally tocomprise and to bring to the size the catalyst(s) mentioned above) mayhave been projected onto the mat before heat treatment of thecombination and the heat treatment may make it possible to polymerizethe binder and the size at the same time.

The strands can also be cut before collecting by a device which is alsoused to draw them, the cut strands being collected on receiving supportsin translational motion, in which case the heat treatment ispreferentially carried out with respect to the cut strands spread outover the receiving supports.

The treatment times for strands collected in the form of rovingsweighing several kilograms are at least 1 hour at temperatures greaterthan approximately 140° C., preferably of the order of 160° C., when thestrands are coated with a composition according to the invention notcomprising specific catalyst(s) (a high temperature promoting theformation of more stable compounds), the treatment time varyingaccording to the shape and the weight of the roving and most of thistime being dedicated to raising the temperature of the mass of glasscontained in the wound package. When the strands coated with acomposition according to the invention not comprising specificcatalyst(s) are collected on one or a number of supports intranslational motion and when the heat treatment is carried out on thesupport or supports, the treatment time is of the order of 15 to 20minutes at temperatures generally greater than approximately 140° C. Thetreatment temperature, whatever the method of collecting the strands,can be lowered by a few tens of degrees (it can decrease by 10 to 30° C.for example and be between 120 and 140° C. approximately) and thetreatment time reduced when the composition coating the strandscomprises at least one specific catalyst as mentioned above.

The strands can also be collected without being subjected to heattreatment, the heat treatment being carried out subsequently. Inparticular, the strands can be collected in the form of wound packagesand can then be extracted from the said wound packages in order to besubjected to additional treatments (for example in order to be cut by adevice which is also used to carry them along mechanically), it beingpossible for the heat treatment to be carried out on the strands before,during or after the additional treatment or treatments (in particular,for the cutting, the heat treatment can be carried out on the device forcollecting the cut strands, and the like).

The sized strands can also be collected without having been heat-treatedand can then be heat-treated after combining with an organic materialduring the preparation of a composite, the said material optionallycomprising at least one catalyst as mentioned above. Depending on theorganic material used, the heat treatment can be accompanied by atreatment with ultraviolet radiation, by a treatment with an electronbeam, and the like. The heat treatment time during the preparation of acomposite is generally at least 2 hours, at temperatures greater thanapproximately 130° C. and preferably of the order of 180-200° C.

The glass strands coated with the size according to the invention and/orobtained according to the process of the invention are coated with anon-polymerized size or with a size polymerized after heat treatment.These strands exhibit a loss on ignition advantageously of less than 3%by weight and preferably of less than 1.5%. The small amount of sizedeposited on the strand makes it possible to greatly reduce the problemsof adhesive bonding between strands, in particular when they arecollected in the form of wound packages, also makes possible betteropening of the strand during impregnation by a material to be reinforcedand is economically advantageous.

The strands obtained according to the invention are easy to handle andcan, after collecting, be found in different forms which may or may notrequire additional stages of treatment of the strands, these stagesbeing carried out before or after the heat treatment and/or thecollecting of the strands. The glass strands can thus be provided in theform of continuous strands, of cut strands, may have been combined inthe form of braids, tapes, mats or networks, which may or may not bewoven, and the like. The strands according to the invention exhibit inparticular good tensile strength properties.

The composites advantageously obtained by combining at least glassstrands according to the invention and at least one organic and/orinorganic material (the level of glass within these composites generallybeing between 30 and 70% by weight) exhibit good mechanical properties,as illustrated in the examples below.

Other advantages and characteristics of the invention will becomeapparent in the light of the following examples giving, by way ofillustration but without implied limitation, sizing compositionsaccording to the invention and characteristics of the strands coatedwith these compositions or characteristics of the composites comprisingthe said strands.

EXAMPLE 1

Filaments with a diameter of 14 microns obtained by drawing molten glassstreams according to the process of the invention are coated with thesize with the following composition, expressed as percentages by weight:

Components of the base system with a molecular mass of less than 750:

Components of the base system with a molecular mass of less than 750:Trimethylolpropane triglycidyl ether⁽¹⁾ 34.0% Diglycidyl ether of1,4-butanediol⁽²⁾ 18.4% 1,2-Epoxyhexadecane⁽³⁾ 29.1%Methyltetrahydrophthalic anhydride⁽⁴⁾ 10.0% Catalyst:1-Methylimidazole⁽⁵⁾  0.5% Additives: Polyethoxylated alkylsilanecoupling agent⁽⁶⁾  8.0%

The filaments are gathered together into strands, which are wound in theform of rovings exhibiting an approximate mass of 13.5 kg, and then therovings are heated at 140° C. for 6 hours.

The strands are then extracted from the wound packages in order tomeasure their tensile strength and their tenacity at break under theconditions defined by ISO Standard 3341. The results on 8 to 10 testspecimens (with the standard deviations shown in brackets) are reportedin the appended Comparative Table I, which also gives the count and theloss on ignition of the strands obtained.

EXAMPLE 2

Filaments with a diameter of 14 microns obtained according to theinvention are coated with the size with the following composition(percentages by weight):

Components of the base system with a molecular mass of less than 750:

Components of the base system with a molecular mass of less than 750:3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexane- 28% carboxylate⁽⁷⁾Mixture based on vinylcyclohexene monoxide⁽⁸⁾ 28% Mixture of phthalicanhydride, of hexahydrophthalic 28% anhydride and of tetrahydrophthalicanhydride⁽⁹⁾ Additives: γ-Methacryloyloxypropyltrimethoxysilane coupling10% agent⁽¹⁰⁾ Isopropyl palmitate textile agent  6%

The ratio r in this composition is 0.7 and this composition exhibits aviscosity of 64 cP at 20° C.

The filaments are gathered into strands, which are wound in the form ofrovings exhibiting an approximate mass of 13.5 kg. The strands thuscollected are not heat-treated.

Composite panels with parallel strands are prepared, in accordance withNF Standard 57152, from the strands obtained exhibiting a count of 320tex. The reinforced resin is “Epoxy LY 556” resin sold under thisreference by the company Ciba-Geigy, to which are added, per 100 partsby weight of epoxy resin, 90 parts of a curing agent sold under thereference “HY 917” by the company Ciba-Geigy and 0.5 parts of anaccelerator sold under the reference “DY 070” by the company Ciba-Geigy.

The panels prepared are then heat-treated and the mechanical propertiesexhibited by these panels, with respect to flexion and shearing, arerespectively measured according to ISO Standard 178 and ISO Standard4585, before ageing and after immersion of these panels in water at 98°C. for 24 hours. The results obtained on 8 to 10 test specimens arereported in the appended Comparative Table II, which gives the type ofresin used for the panels, the flexural strength at break for a level ofglass adjusted to 100%, before and after ageing, and the shear strengthat break before and after ageing. The standard deviations are shown inbrackets.

EXAMPLE 3

The procedure is the same as in Example 2, the heat treatment, however,being carried out with respect to the strand wound packages and not withrespect to the composite panels. The strand rovings obtained in Example2 are thus heated, in the present example, at 160° C. for 8 hours. Nodeformation of these rovings is observed. The results obtained withrespect to composite panels in the present example are reported in TableII.

The tensile strength and tenacity at break of the heat-treated strandsextracted from the wound packages are also measured, as in Example 1.The results are reported in Table I.

EXAMPLE 4

Filaments with a diameter of 14 microns obtained according to theinvention are coated with the size with the following composition(percentages by weight):

Components of the base system with a molecular mass of less than 750:

Components of the base system with a molecular mass of less than 750:3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexane- 25.0% carboxylate⁽⁷⁾Diglycidyl ether of 1,4-butanediol⁽²⁾ 10.0% 2-Ethylhexyl glycidylether⁽¹¹⁾ 20.0% Methyl-5-norbornene-2,3-dicarboxylic anhydride⁽¹²⁾ 36.5%Catalyst: 1-Methylimidazole⁽⁵⁾  0.5% Additives: Polyethoxylatedalkylsilane coupling agent⁽⁶⁾  8.0%

The ratio r in this composition is 1.3 and this composition exhibits aviscosity of 72 cP at 20° C.

The filaments are gathered together into strands, which are wound in theform of rovings weighing approximately 13.5 kg, and are then heated at160° C. for 6 hours. The tensile strength and tenacity at break of thestrands are then measured, as in Example 1 (Table I). The resistance toabrasion of the strands is also evaluated by weighing the amount offlock formed after passing the strands over a series of rods. Fordifferent strands coated with the polymerized size described in thepresent example, the amount of flock on conclusion of the test is of theorder of 1 mg per kg of strand tested.

By way of comparison, strands coated with an aqueous size based on anemulsion containing epoxy resin, silanes and surfactants, these strandsbeing dried according to normal methods, can form 200, indeed 500, mg offlock per kg of strand.

EXAMPLE 5

Filaments with a diameter of 10 microns obtained according to theinvention are coated with the size with the following composition(percentages by weight):

Components of the base system with a molecular mass of less than 750:

Components of the base system with a molecular mass of less than 750:Diglycidyl ether on a novolak phenol base⁽¹³⁾ 25.0% Diglycidyl ether of1,4-butanediol⁽²⁾ 10.0% 2-Ethylhexyl glycidyl ether⁽¹¹⁾ 16.5%Methyltetrahydrophthalic anhydride⁽⁴⁾ 40.0% Catalyst:1-Methylimidazole⁽⁵⁾  0.5% Additives: Polyethoxylated alkylsilanecoupling agent⁽⁶⁾  8.0%

The filaments are gathered together into strands, which are wound in theform of cakes weighing approximately 7 kg, and are then heated at 140°C. for 6 hours. The tensile strength and tenacity at break of thestrands are then measured, as in Example 1 (Table I).

EXAMPLE 6

Filaments obtained according to the invention are coated with a sizewith the following composition (percentages by weight):

Components of the base system with a molecular mass of less than 750:

Components of the base system with a molecular mass of less than 750:Trimethylolpropane triglycidyl ether⁽¹⁾ 24% 2-Ethylhexyl glycidylether⁽¹¹⁾ 24% Methyl-5-norbornene-2,3-dicarboxylic anhydride⁽¹²⁾ 40%Additives: γ-Methacryloyloxypropyltrimethoxysilane 12% couplingagent⁽¹⁰⁾

The ratio r in this composition is 1.9.

The filaments are gathered together into strands, which are wound in theform of rovings. The collected strands are not heat-treated.

Composite panels are prepared from these strands, which are easilyextracted from the wound packages obtained, in the same way as inExample 2 and are then heat-treated and the mechanical properties ofthese panels, measured under the same conditions as in Example 2, arereported in Table II.

EXAMPLE 7

The procedure is the same as in Example 6, use being made of anidentical sizing composition but which comprises a lower level ofcoupling agent (11.6% instead of 12%) and which additionally comprises acatalyst in the form of a 2,4,6-tridimethylaminomethylphenol, sold underthe reference “Protex NX3” by the company Protex, at levels of 0.4% byweight of the composition.

The results are reported in Table II.

EXAMPLE 8

Filaments obtained according to the invention are coated with the sizewith the following composition (percentages by weight):

Components of the base system with a molecular mass of less than 750:

Components of the base system with a molecular mass of less than 750:Tetraglycidyl ether of 4,4′-diamino- 20.0% diphenylmethane⁽¹⁴⁾ Cresylglycidyl ether⁽¹⁵⁾ 15.0% Diglycidyl ether of cyclohexane-dimethanol⁽¹⁶⁾ 8.0% Methylhexahydrophthalic anhydride⁽¹⁷⁾ 42.0% Catalyst:2-Propylimidazole⁽¹⁸⁾  0.3% Additives:γ-Methacryloyloxypropyltrimethoxysilane coupling  8.7% agent(10)γ-Glycidoxypropyltrimethoxysilane coupling  6.0% agent(19)

The ratio r in this composition is 1.68.

The procedure is then as in Example 6, use being made in the compositepanels prepared, in place of the epoxy resin, of a polyester resin “M402”, sold under this reference by the company Ciba-Geigy, to which areadded, per 100 parts by weight of polyester resin, 20 parts of asoftening agent sold under the reference “F 8010 C” by the companyCiba-Geigy, 16.5 parts of styrene and 1.5 parts of an accelerator soldunder the reference “THM 60” by the company Ciba-Geigy.

The results are reported in Table II.

EXAMPLE 9

The procedure is the same as in Example 6, the sizing composition usedbeing replaced by the following composition (percentages by weight):

Components of the base system with a molecular mass of less than 750:

Components of the base system with a molecular mass of less than 750:Bisphenol A diglycidyl ether⁽²⁰⁾ 21.0% Cresyl glycidyl ether⁽¹⁵⁾ 25.0%Methylhexahydrophthalic anhydride⁽¹⁷⁾ 42.0% Catalyst: Organometallicamine in polyglycols⁽²¹⁾  0.4% Additives:γ-Methacryloyloxypropyltrimethoxysilane coupling 11.6% agent⁽¹⁰⁾

The ratio r in this composition is 1.98.

The procedure is then as in Example 6. The results are reported in TableII.

EXAMPLE 10

Filaments obtained according to the invention are coated with the sizewith the following composition (percentages by weight):

Components of the base system with a molecular mass of less than 750:

Components of the base system with a molecular mass of less than 750:Diglycidyl ether of cyclohexanedimethanol⁽¹⁶⁾ 10.0% 2-Ethylhexylglycidyl ether⁽¹¹⁾ 14.0% Methylhexahydrophthalic anhydride⁽¹⁷⁾ 40.0%

Components of the base system with a molecular mass greater than 750:

Components of the base system with a molecular mass greater than 750:Triglycidyl ether on an aliphatic polyol base 20.0% with an averagemolecular mass of 1950⁽²²⁾ Catalyst: 2-Propylimidazole⁽¹⁸⁾  0.4%Additives: g-Methacryloyloxypropyltrimethoxysilane coupling 11.6%agent⁽¹⁰⁾ Isopropyl palmitate textile agent  4.0%

The ratio r in this composition is 2.96.

The filaments are gathered together into strands, which are wound in theform of rovings, and are then heated at 145° C. for 8 hours. The tensilestrength and tenacity at break of the strands are then measured as inExample 1 (Table I).

Composite panels are prepared from the strands obtained, which areeasily extracted from the wound packages, in the same way as in Example3, use being made, however, as resin, in place of the epoxy resin LY556, of an epoxy resin “CY 205”, sold under this reference by thecompany Ciba-Geigy, to which are added, per 100 parts by weight of epoxyresin, 32 parts by weight of a curing agent sold under the reference “HT972” by the company Ciba-Geigy.

The mechanical properties of the panels obtained are measured as inExample 2, before ageing and after immersion of the panels in water at98° C. for, this time, 72 hours (Table II)

EXAMPLE 11

The procedure is as in Example 2, use being made of an identical sizingcomposition but which comprises a lower level of3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (9.3% insteadof 28%), a lower level of the mixture based on vinylcyclohexene monoxide(18.7% instead of 28%) and a higher level of the mixture of phthalicanhydride, of hexahydrophthalic anhydride and of tetrahydrophthalicanhydride (58% instead of 28%). The ratio r in this composition is 2.84and this composition exhibits a viscosity of 76 cP at 20° C.

The results are reported in Table II.

EXAMPLE 12

The procedure is as in Example 3, the sizing composition explained inExample 11 being used.

The results are reported in Tables I and II.

The resistance to abrasion of the strands is also measured as in Example4. The amount of flock weighed on conclusion of the test is 99 mg per kgof strand.

EXAMPLE 13

Filaments with a diameter of 14 microns obtained according to theinvention are coated with the size with the following composition(percentages by weight):

Components of the base system with a molecular mass of less than 750:

Components of the base system with a molecular mass of less than 750:3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexane-  9.25% carboxylate⁽⁷⁾Mixture based on vinylcyclohexene monoxide⁽⁸⁾  9.25% Mixture of phthalicanhydride, of hexahydrophthalic 55.5% anhydride and oftetrahydrophthalic anhydride⁽⁹⁾ Additives:γ-Methacryloyloxypropyltrimethoxysilane coupling 20% agent⁽¹⁰⁾ Isopropylpalmitate textile agent  6%

The ratio r in this composition is 4.19 and this composition exhibits aviscosity of 62 cP at 20° C.

The filaments are gathered together into strands, which are wound in the35 form of rovings weighing approximately 13.5 kg, and are then heatedat 160° C. for 8 hours. The tensile strength and tenacity at break ofthe strands are then measured, as in Example 1 (Table I).

The resistance to abrasion of the strands is also measured as in Example4. The amount of flock weighed on conclusion of the test is 57 mg per kgof strand.

COMPARATIVE EXAMPLE

The mechanical characteristics of the composites obtained using thestrands described in Examples 2, 3 and 6 to 12 are compared with themechanical characteristics of the composites obtained using referencestrands coated with an aqueous size based on an emulsion containingepoxy resin, silanes and surfactants, the latter composites beingprepared in the same way as in Examples 8 (the heat treatment, however,being carried out with respect to the strand wound packages and not withrespect to the composite panels) and 10 (the heat treatment of thestrands being, however, carried out at a higher temperature)respectively, and the mechanical properties of the latter composites,measured as in Examples 2 and 10 respectively, being reported inComparative Table II.

It is observed, in the preceding examples, that the strands coated withsize according to the invention are easy to handle, whether or not theyhad been heat-treated, and exhibit good tensile strength properties.Remarkably and advantageously, the tensile strength properties of thestrands coated with size according to the invention are better after thebeginning of ageing in a humid environment than those obtained beforeageing of the sized strands.

The strands obtained according to the invention moreover exhibit a lowloss on ignition and good resistance to abrasion and make it possible toefficiently reinforce organic and/or inorganic materials.

The low levels of flock obtained during the tests of resistance toabrasion of the strands and the good tensile strength properties of thestrands also make it possible to say that the strands obtained accordingto the invention exhibit good integrity. The strands obtained also givegood texturing results.

The strands coated with size according to the invention moreover make itpossible to obtain composites exhibiting mechanical properties which areas good as those of the composites obtained from strands coated withconventional aqueous sizes.

The glass strands according to the invention can be used in variousapplications, for example in textile applications, such as themanufacture of warps by warping, or directly in reinforcingapplications, such as the reinforcement of organic materials (forexample plastics) or inorganic materials (for example cement materials),in order to obtain composite products.

(1) Sold under the reference “Heloxy 5048” by the company Shell

(2) Sold under the reference “Heloxy 67” by the company Shell

(3) Sold under the reference “UVR 6216” by the company Union Carbide

(4) Sold under the reference “HY 917” by the company Ciba-Geigy

(5) Sold under the reference “DY 070” by the company Ciba-Geigy

(6) Sold under the reference “Silquest A 1230” by the company OSI

(7) Sold under the reference “UVR 6110” by the company Union Carbide

(8) Sold under the reference “UVR 6200” by the company Union Carbide

(9) Sold under the reference “HY 905” by the company Ciba-Geigy

(10) Sold under the reference “Silquest A 174” by the company OSI

(11) Sold under the reference “Heloxy 116” by the company Shell

(12) Sold under the reference “HY 906” by the company Ciba-Geigy

(13) Sold under the reference “Araldite PY 307” by the companyCiba-Geigy

(14) Sold under the reference “Araldite MY 722” by the companyCiba-Geigy

(15) Sold under the reference “Heloxy 62” by the company Shell

(16) Sold under the reference “Heloxy 107” by the company Shell

(17) Sold under the reference “HY 1102 BD” by the company Ciba-Geigy

(18) Sold under the reference “Actiron NXJ 60” by the company Protex

(19) Sold under the reference “Silquest A 187” by the company OSI

(20) Sold under the reference “Araldite GY 250” by the companyCiba-Geigy

(21) Sold under the reference “DY 071” by the company Ciba-Geigy

(22) Sold under the reference “Heloxy 84” by the company Shell

COMPARATIVE TABLE I Ex. 1 Ex. 3 Ex. 4 Ex. 5 Ex. 10 Ex. 12 Ex. 13 Count(tex) 320 320 320 84 320 320 320 Loss on 0.93 0.58 0.82 0.56 0.42 0.390.40 ignition (%) Tensile strength at break (kgf) 16.5 18.2 19.0 4.717.2 18.7 18.1 σ (0.8) (1.1) (0.7) (0.2) (0.6) (0.8) (1.4) Tenacity 48.657.8 57.0 53.3 53.6 55.2 56.1 (g/tex) σ (2.3) (3.4) (2.0) (2.8) (2.0)(2.3) (4.4)

COMPARATIVE TABLE II Compa- Compa- Ex. Ex. Ex. rative rative Ex. 2 Ex. 3Ex. 6 Ex. 7 Ex. 8 Ex. 9 10 11 12 Ex. Ex. Resin used Epoxy Epoxy EpoxyEpoxy Polyester Epoxy Epoxy Epoxy Epoxy Polyester Epoxy Flexuralstrength at break for 100% glass (MPa) *Before ageing 2341 2122 22072361 2268 2274 2022 2379 2334 2440 2280 σ (65) (62) (46) (63) (68) (66)(83) (43) (49) (70) (40) *After ageing 2241 1767 1822 1758 1406 18831408 2211 1977 1370 1400 σ (89) (65) (29) (81) (38) (69) (67) (99) (85)(40) (20) Shear strength at break (MPa) *Before ageing 64.7 86.0 56.069.4 59.8 48.8 56.3 85.1 68.6 56.5 69.5 σ (1.0) (0.5) (0.9) (0.8) (0.4)(0.8) (0.9) (1.4) (1.8) (1.0) (1.0) *After ageing 42.3 72.1 49.4 50.828.6 (49.0 41.2 64.7 49.0 25.0 40.0 σ (5.1) (1.3) (1.3) (1.4) (0.2)(0.5) (0.7) (2.1) (1.6) (0.5) (0.4)

What is claimed is:
 1. Glass strand coated with a sizing compositioncomposed of a solution with a viscosity of less than or equal to 400 cPcomprising less than 5% by weight of solvent and comprising at least onethermally polymerizable and/or crosslinkable base system, the said basesystem comprising at least 60% by weight of components with a molecularmass of less than 750 and comprising at least 60% by weight of amixture: of component(s) exhibiting at least one epoxy reactivefunctional group, and of component(s) exhibiting at least one anhydridereactive functional group.
 2. Glass strand according to claim 1, whereinthe base system represents between 60 and 100% by weight of the sizingcomposition.
 3. Coated glass strand obtained by thermally polymerizingthe glass strand coated with a sizing composition according to claim 2.4. Glass strand according to claim 1, wherein the compositionadditionally comprises at least one catalyst which facilitates theopening of the anhydride or epoxy functional groups under the effect ofheat.
 5. Coated glass strand obtained by thermally polymerizing theglass strand coated with a sizing composition according to claim
 4. 6.Glass strand according to claim 1, wherein the composition additionallycomprises at least one film-forming agent in proportions of between 0and 10% by weight.
 7. Coated glass strand obtained by thermallypolymerizing the glass strand coated with a sizing composition accordingto claim
 6. 8. Glass strand according to claim 1, characterized in thatthe base system is composed solely of components exhibiting at least oneepoxy reactive functional group and components exhibiting at least oneanhydride reactive functional group.
 9. Coated glass strand obtained bythermally polymerizing the glass strand coated with a sizing compositionaccording to claim
 8. 10. Glass strand according to claim 1, wherein thecomposition additionally comprises at least one coupling agent inproportions of between 0 and 25% by weight.
 11. Coated glass strandobtained by thermally polymerizing the glass strand coated with a sizingcomposition according to claim
 10. 12. Glass strand according to claim1, wherein the composition additionally comprises at least one textileagent in proportions of between 0 and 15% by weight.
 13. Coated glassstrand obtained by thermally polymerizing the glass strand coated with asizing composition according to claim
 12. 14. Coated glass strandobtained by thermally polymerizing the glass strand coated with a sizingcomposition according to claim
 1. 15. Composite comprising at least oneorganic and/or inorganic material and sized glass strands, wherein thecomposite comprises at least in part sized glass strands according toclaim
 14. 16. Composite comprising at least one organic and/or inorganicmaterial and sized glass strands, wherein the composite it comprises atleast in part sized glass strands according to claim
 1. 17. Sizingcomposition for a glass strand composed of a solution with a viscosityof less than or equal to 400 cP comprising less than 5% by weight ofsolvent and comprising at least one thermally polymerizable and/orcrosslinkable base system, the said base system comprising at least 60%by weight of components with a molecular mass of less than 750 andcomprising at least 60% by weight of a mixture: of component(s)exhibiting at least one epoxy reactive functional group, and ofcomponent(s) exhibiting at least one anhydride reactive functionalgroup.
 18. Process for the production of sized glass stands according towhich a multiplicity of molten glass streams, flowing from amultiplicity of orifices arranged at the base of one or a number ofdies, is drawn in the from of one or a number of sheets of continuousfilaments and then the filaments are gathered together in one or anumber of strands which are collected on a moving support, the saidprocess comprising the deposition at the surface of the filaments,during drawing and before gathering together the filaments into strands,of a sizing composition composed of a solution with a viscosity of lessthan or equal of 400 cP comprising less than 5% by weight of solvent andcomprising at least one thermally polymerizable and/or crosslinkablebase system, the said base system comprising at least 60% by weight ofcomponents with a molecular mass of less than 750 and comprising atleast 60% of weight of a mixture: of component(s) exhibiting at leastone epoxy reactive functional group, and of component(s) exhibiting atleast one anhydride reactive functional group.
 19. Process according toclaim 18, wherein the strands are collected in the form of woundpackages on a rotating support, the crossing angle of the wound packagesbeing at least equal to 1.5°.
 20. Process according to claim 18, whereinthe sizing composition is subjected to a heat treatment during or aftercollecting the strands coated with the said composition.
 21. Processaccording to claim 18, wherein the sized strands collected are broughtinto contact with an organic material to be reinforced, beforesubjecting the combination to a heat treatment, so as to obtain acomposite.